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WO2016077361A1 - Hydrogénation électrocatalytique de l'acide muconique - Google Patents

Hydrogénation électrocatalytique de l'acide muconique Download PDF

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WO2016077361A1
WO2016077361A1 PCT/US2015/059974 US2015059974W WO2016077361A1 WO 2016077361 A1 WO2016077361 A1 WO 2016077361A1 US 2015059974 W US2015059974 W US 2015059974W WO 2016077361 A1 WO2016077361 A1 WO 2016077361A1
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acid
hexene
dioic
combination
cathode
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Jean-Philippe Tessonnier
John Edward MATTHIESEN
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Iowa State University Research Foundation Inc ISURF
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Iowa State University Research Foundation Inc ISURF
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • muconic acid is an unsaturated dicarboxylic acid, hexe-2,4-dienedoic acid, which can exist in three isomeric forms.
  • Muconic acid has garnered significant interest due to its potential use as a platform chemical for the production of several valuable consumer bio- plastics including nylon 6,6, polyurethane (via an adipic acid intermediate), and polyethylene terephthalate (PET) (via a terephthalic acid intermediate).
  • Adipic acid is produced mainly from petrochemicals like benzene. Because of the strong environmental impact of the production processes and the dependence on fossil resources, biotechnological production processes have been extensively explored.
  • C. Weber et al. Appl. Env. Microbiol. , 71 , 8421 (2012) disclose the use of engineered Saccharomyces cerevisiae strain expressing a heterologous biosynthetic pathway converting glucose into cis,cis- muconic acid via the intermediate 3-dehydroshikimate of the aromatic amino acid biosynthesis pathway via protocatechuic acid and catechol, which can potentially be chemically hydrogenated to adipic acid.
  • Eng., 15, 55 (2013) have reported a three-step synthetic, composite pathway including importing the enzymes dehydroshikimate dehydratase from Podospora anserina, protocatechuic acid decarboxylase from Enterobacter cloacae, and catechol 1 ,2-dioxygenase from Candida albicans into yeast. Further genetic modifications guided by metabolic modeling and feedback inhibition mitigation were introduced to increase precursor availability that led to a final titer of nearly 141 mg/L muconic acid in a shake-flask culture, a value nearly 24- fold higher than obtained from the initial strain.
  • the hydrogenation of muconic acid to adipic acid presents many of the difficulties encountered in the hydrogenation of edible oils and fats.
  • the majority of commercially hydrogenated oils and fats are processed with batch reactor equipment using high temperatures, chemical catalysts, and hydrogen gas supplied to the reactor at elevated pressures.
  • the hydrogenation catalysts used include Raney and supported nickel catalysts, promoted nickel catalysts containing palladium, copper, or zirconium, and copper chromite catalysts.
  • the rate of hydrogenation is dependent on the reaction temperature, the nature of the oil or fat, the activity and concentration of the catalyst, and the rate at which hydrogen gas and unsaturated oil or fat are supplied to the hydrogenation reactor.
  • Typical reaction pressures and temperatures are in the range of 10-60 bar and 150°-225°C, respectively. These elevated temperatures and pressures are required to solubilize sufficiently high concentrations of hydrogen gas in the oil/catalyst or fat/catalyst reaction medium so that the hydrogenation reaction proceeds at acceptably high rates.
  • Electrocatalytic hydrogenations of unsaturated organic compounds using Raney nickel or similar low hydrogen overvoltage catalysts as cathode materials can employ less rigorous conditions, and have been reported by a number of investigators (e.g., T. Chiba et al., Bull. Chem. Soc. Jpn., 56, 719 (1983); L. L. Miller et al., J. Org.Chem., 43, 2059 (1978); L. V. Kirilyus et al., Sov. Electrochem., 15, 1330 (1979); K. Park et al., J. Electrochem. Soc, 132, 1850 (1985)).
  • Pintauro U.S. Patent No. 5,225,581 discloses a two-phase electrocatalytic process for hydrogenating unsaturated fatty acids or triglycerides using hydrogen generated electrolytically on a high surface area, low hydrogen overvoltage catalytic material used as the cathode.
  • this process was not disclosed to be useful to hydrogenate unsaturated alkene dioic acids, either in purified form, or in situ as formed in the
  • the present invention provides an electrocatalytic method to prepare 3-hexene-l,6-dioic acid, 2-hexene-l,6-dioic acid, adipic acid, or a combination thereof, from muconic acid.
  • the method includes passing current through a catalytic cathode in a reactor including an aqueous acidic solution including muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid.
  • the hydrogenation of the muconic acid yields a product including 3-hexene-l,6-dioic acid, 2-hexene-l,6-dioic acid, adipic acid, or a mixture thereof.
  • the present invention provides an electrocatalytic method to prepare adipic acid from muconic acid.
  • the method includes passing current through a catalytic cathode including Pd on carbon, wherein the catalytic cathode is in a reactor including an aqueous acidic solution including muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid so as to yield a product including adipic acid with a selectivity (e.g., a selectivity toward adipic acid) of about 40% to about 100%.
  • a selectivity e.g., a selectivity toward adipic acid
  • the present invention provides an electrocatalytic method to prepare £raws-3-hexene-l,6-dioic acid from muconic acid.
  • the method includes passing current through a catalytic cathode including Cu, Fe, Pb, Sn, Ti, Zn, or a combination thereof, wherein the catalytic cathode is in a reactor including an aqueous acidic solution including muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid so as to yield a product including ?raws-3-hexene-l ,6-dioic acid with a selectivity of about 50% to about 100%.
  • the present invention provides a method of forming a polymer.
  • the method includes polymerizing 2-hexene-l,6-dioic acid, the 3-hexene-l ,6-dioic acid, or a combination thereof, with another compound, to form a polymer.
  • the present invention provides a method of forming a polymer, including polymerizing the 2-hexene-l,6-dioic acid, the 3- hexene-l,6-dioic acid, or a combination thereof, with a compound having the structure H2N-(Ci-C2o)alkylene-NH2 or a salt thereof, wherein the (Ci-C2o)alkyl group is substituted or unsubstituted, to form a polymer.
  • the present invention provides a polymer including a repeating group having the structure:
  • the present invention provides polymer including a repeating group having the structure:
  • Various embodiments have certain advantages over other methods of hydrogenating muconic acid. For example, in various embodiments, hydrogen and catalyst can be used more efficiently, thus requiring lower catalyst loading of the reactor. In various embodiments, there is little free hydrogenation gas present, thus reducing the risk of explosion and fire. In various embodiments, hydrogen and catalyst can be used more efficiently, thus requiring lower catalyst loading of the reactor. In various embodiments, there is little free hydrogenation gas present, thus reducing the risk of explosion and fire. In various
  • the concentration of hydrogen on the catalyst metal surface can be easily controlled by adjusting the applied current (or applied electric potential), which can lead to improved product selectivity.
  • the operating temperatures can be low, thus minimizing thermal degradation of the reactants and products or unwanted homogeneous side reactions.
  • corrosion of the metal catalyst can be less, thus reducing or eliminating the presence of metal ion contaminants in the hydrogenated product.
  • the method can form 3-hexenedioic acid from muconic acid, such as trans-3-hexenedioic acid, with higher selectivity, higher conversion, or a combination thereof, as compared to other methods.
  • the method can form adipic acid from muconic acid with higher selectivity, higher conversion, or a combination thereof, as compared to other methods.
  • the method can include at least partially simultaneously forming muconic acid from yeast fermentation and performing electrocatalytic hydrogenation on the muconic acid directly in the fermentation broth, such that the yeast survives during the electrocatalytic hydrogenation and continues to generate muconic acid.
  • the metal in the cathode can be less sensitive to impurities in the aqueous media as compared to other methods of hydrogenation, or can have no sensitivity to such impurities, such as compounds formed in the fermentation broth during the production of muconic acid, allowing the electrocatalytic hydrogenation method to be performed using impure aqueous media or using the fermentation broth.
  • electrocatalytic hydrogenation can be polymerized.
  • the polymer formed can have useful properties.
  • FIG. 1 is a schematic drawing of a three-electrode
  • electrochemical cell (1) according to various embodiments.
  • FIG. 2A-B are bar graphs depicting the conversion, selectivity and Faradaic efficiency using the lead/Pt coil electrocatalysts when converting muconic acid (MA) to 3-hexene-l,6-dioic acid (HDA), according to various embodiments.
  • FIG. 3 illustrates the integrated conversion of glucose to UPA
  • FIGS. 4A-B illustrate conversion of MA to HDA in the fermentation broth, in accordance with various embodiments.
  • FIGS. 5A-B illustrate MA conversion and HDA selectivity versus reaction time of electrocatalytic hydrogenation (ECH) of model solutions of MA with varying pH, in accordance with various embodiments.
  • FIG. 6 illustrates l U NMR spectra of HDA subjected to -1.5 V for 2 h before (A) and after (B) reaction, in accordance with various embodiments.
  • FIGS. 7A-B illustrate MA conversion and HDA selectivity versus reaction time during ECH of model solutions of MA at varying potentials, in accordance with various embodiments.
  • FIG. 8 illustrates a l U NMR of irarcs-3-hexenedioic acid (?3HDA) extracted from the fermentation broth. (1) before crystallization and (2) after crystallization, in accordance with various embodiments.
  • FIG. 9A illustrates 1) nylon 6,6 and 2) bio-based unsaturated nylon 6,6 (UPA 6,6), in accordance with various embodiments.
  • FIG. 9B illustrates polymer blends of adipic acid and HDA, in accordance with various embodiments.
  • FIG. 10 illustrates an overlay from gel permeation
  • FIG. 11 illustrates thermal gravimetric analysis of nylon 6,6
  • FIG. 12 illustrates differential scanning calorimetry results for nylon 6,6 and UPA 6,6, in accordance with various embodiments.
  • FIG. 13 illustrates a master curve of the dynamic shear moduli G' and G" for UPA 6,6 over the temperature range 50-150 °C, in accordance with various embodiments.
  • FIG. 14 illustrates an X-ray diffraction (XRD) pattern of UPA 6,6 and nylon 6,6, in accordance with various embodiments.
  • FIG. 15 illustrates concentrations of MA isomers over time at low pH, in accordance with various embodiments.
  • FIG. 16 illustrates theoretical potentials for the formation of hydrogen (HER), ds-3-hexenedioic acid (c3HDA), fraws-3-hexenedioic acid (?3HDA), cis-2-hexenedioic acid (c2HDA), ?raws-2-hexenedioic acid (?2HDA), and AA from cis,trans-muconic acid (c?MA) as a function of pH, in accordance with various embodiments.
  • HER hydrogen
  • c3HDA ds-3-hexenedioic acid
  • ?3HDA fraws-3-hexenedioic acid
  • cis-2-hexenedioic acid c2HDA
  • ?raws-2-hexenedioic acid ?2HDA
  • AA cis,trans-muconic acid
  • FIG. 17 illustrates a volcano plot showing the current exchange densities (HER activities) achieved as a function of the free energy of hydrogen adsorption AG H of the metals, in accordance with various embodiments.
  • FIGS. 18A-0 illustrate conversion, selectivity, and faradaic efficiencies during ECH of ciMA in 1 % formic acid solution with various low hydrogen overpotential metals at various voltages, in accordance with various embodiments.
  • FIGS. 19A-L illustrate conversion, selectivity, and faradaic efficiencies of ECH of ciMA in 1 % formic acid solution with various high hydrogen overpotential metals at various voltages, in accordance with various embodiments.
  • FIGS. 20A-C illustrate light microscope images of the Pb electrode strip (A) after cleaning with a kimwipe, (B) after electropolishing, and (B) after ECH of ctMA, in accordance with various embodiments.
  • FIGS. 21A-C illustrate conversion (A), selectivity (B), and faradaic efficiency (C) of ECH of ctMA with electro-polished Pb at -1.17 V in a 1% formic acid solution, in accordance with various embodiments.
  • FIG. 22A illustrates cyclic voltammetry of Pd/C in 0.5 M NaOH.
  • FIG. 22B illustrates conversion and selectivity of ECH of ctMA in 1% formic acid solution at -1.17 V
  • FIG. 22C illustrates the faradaic efficiency during ECH of ctMA in 1% formic acid solution at -1.17 V.
  • FIG. 22D illustrates the turn over frequency of Pd/C catalyst during ECH of ctMA in 1% formic acid solution at -1.17 V.
  • FIGS. 23A-F illustrate ctMA and ?3HDA concentration profiles during simultaneous fermentation and ECH, in accordance with various embodiments.
  • a comma can be used as a delimiter or digit group separator to the left or right of a decimal mark; for example, "0.000,1" is equivalent to "0.0001.”
  • the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
  • the term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.
  • organic group refers to any carbon- containing functional group.
  • Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups.
  • oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group
  • a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester such as an alkyl and aryl sulfide group
  • Non-limiting examples of organic groups include OR, OOR, OC(0)N(R) 2 , CN, CF 3 , OCF 3 , R, C(O), methylenedioxy,
  • substituted refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non- hydrogen atoms.
  • functional group refers to a group that can be or is substituted onto a molecule or onto an organic group.
  • substituents or functional groups include, but are not limited to, a halogen (e.g., F, CI, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups.
  • a halogen e.g., F, CI, Br, and I
  • an oxygen atom in groups such as hydroxy groups
  • Non-limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR, OC(0)N(R) 2 , CN, NO, N0 2 , ON0 2 , azido, CF 3 , OCF 3 , R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R) 2 , SR, SOR, S0 2 R, S0 2 N(R) 2 , SO3R, C(0)R, C(0)C(0)R, C(0)CH 2 C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R) 2 , OC(0)N(R) 2 , C(S)N(R) 2 , (CH 2 ) 0 - 2 N(R)C(O)R, (CH 2 ) 0 - 2 N(R)N(R) 2 , N(R)N(R)
  • R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (Ci-Cioo)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl.
  • alkyl refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • alkyl encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl.
  • Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
  • alkenyl refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms.
  • alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms.
  • acyl refers to a group containing a carbonyl moiety wherein the group is bonded via the carbonyl carbon atom.
  • the carbonyl carbon atom is bonded to a hydrogen forming a "formyl” group or is bonded to another carbon atom, which can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like.
  • An acyl group can include 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group.
  • An acyl group can include double or triple bonds within the meaning herein.
  • An acryloyl group is an example of an acyl group.
  • An acyl group can also include heteroatoms within the meaning herein.
  • a nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein.
  • Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups and the like.
  • the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a "haloacyl" group.
  • An example is a trifluoro acetyl group.
  • aryl refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • aryl groups contain about 6 to about 14 carbons in the ring portions of the groups.
  • Aryl groups can be unsubstituted or substituted, as defined herein.
  • Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof.
  • amine refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)3 wherein each group can independently be H or non-H, such as alkyl, aryl, and the like.
  • Amines include but are not limited to R-NH 2 , for example, alkylamines, arylamines,
  • alkylarylamines R 2 NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like.
  • amine also includes ammonium ions as used herein.
  • amino group refers to a substituent of the form -NH 2 , -NHR, -NR 2 , -NR3 "1” , wherein each R is independently selected, and protonated forms of each, except for -NR3 "1" , which cannot be protonated. Accordingly, any compound substituted with an amino group can be viewed as an amine.
  • An “amino group” within the meaning herein can be a primary, secondary, tertiary, or quaternary amino group.
  • alkylamino includes a monoalkylamino, dialkylamino, and trialkylamino group.
  • halo means, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.
  • M n number- average molecular weight
  • weight- average molecular weight refers to M w , which is equal to ⁇ Mi3 ⁇ 4 / ⁇ Mi3 ⁇ 4, where 3 ⁇ 4 is the number of molecules of molecular weight Mi.
  • the weight- average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.
  • solvent refers to a liquid that can dissolve a solid, liquid, or gas.
  • solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
  • polymer refers to a molecule having at least one repeating unit and can include copolymers.
  • salts having a positively charged counterion can include any suitable positively charged counterion.
  • the counterion can be ammonium(NH4 + ), or an alkali metal such as sodium (Na + ), potassium (K + ), or lithium (Li + ).
  • the counterion can have a positive charge greater than +1, which can in some embodiments complex to multiple ionized groups, such as Zn 2+ , Al 3+ , or alkaline earth metals such as Ca 2+ or Mg 2+ .
  • salts having a negatively charged counterion can include any suitable negatively charged counterion.
  • the counterion can be a halide, such as fluoride, chloride, iodide, or bromide.
  • the counterion can be nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide, permanganate.
  • the counterion can be a conjugate base of any carboxylic acid, such as acetate or formate.
  • a counterion can have a negative charge greater than - 1 , which can in some embodiments complex to multiple ionized groups, such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide, or oxalate.
  • ionized groups such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide, or oxalate.
  • polymers described herein can terminate in any suitable way.
  • the polymers can terminate with an end group that is independently chosen from a suitable polymerization initiator, -H, -OH, a substituted or unsubstituted (Ci-C2o)hydrocarbyl (e.g., (Ci-Cio)alkyl or (C 6 - C 2 o)aryl) interrupted with 0, 1, 2, or 3 groups independently selected from -0-, substituted or unsubstituted -NH-, and -S-, a poly(substituted or unsubstituted (Ci-C 2 o)hydrocarbyloxy), and a poly( substituted or unsubstituted (Ci- C 2 o)hydrocarbylamino).
  • a suitable polymerization initiator -H, -OH
  • a substituted or unsubstituted (Ci-C2o)hydrocarbyl e.g., (Ci-Cio)alkyl or (C 6 - C 2 o
  • the present invention provides an electrocatalytic method to hydrogenate muconic acid to yield a product including the hydrogenated product 3-hexene-l,6-dioic acid, 2-hexene-l,6-dioic acid, adipic acid, or combinations thereof, with both a high conversion of muconic acid to the hydrogenated products and a high selectivity for conversion to one or both of the hydrogenated products.
  • 3-Hexene- 1 ,6-dioic acid or 2-hexene- 1 ,6- dioic acid can be useful in preparing nylon 6,6 analogs (e.g., which can be designated as bio-based unsaturated nylon 6,6 or UPA 6,6) with unique or adjustable properties.
  • the unsaturated bond at the 2- or 3 -position can be functionalized before or after copolymerization.
  • the present invention provides an electrocatalytic method to prepare 3-hexene-l,6-dioic acid, 2-hexene- 1,6-dioic acid, adipic acid, or a combination thereof, from muconic acid.
  • the method can include passing current through a catalytic cathode in a reactor including an aqueous acidic solution including muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydro genate the muconic acid to yield a product including 3-hexene- 1,6-dioic acid, 2-hexene- 1 ,6-dioic acid, adipic acid, or a mixture thereof.
  • the adsorbed hydrogen on the surface of the catalyst can react with the muconic acid to yield the saturated product (adipic acid) or partially saturated product (3-hexene- 1 ,6- dioic acid or 2-hexene- 1,6-dioic acid, with cis or trans configurations possible for both) as shown in Scheme 2.
  • the hydrogenation can be carried out at any suitable temperature and pressure.
  • the hydrogenation can be conducted under ambient conditions of temperature and pressure, such as about 20° to about 30°C and at about 1 atm, for a time sufficient to complete the desired transformation, e.g., about 0.5 h to about 24 h, about 1 h to about 5 h, or about 1 h or less, or less than, equal to, or greater than about 2 h, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or about 24 h or more.
  • the hydrogenation can be carried out in an acidified aqueous medium, such as water or even a yeast fermentation broth (e.g., medium) employed to prepare the muconic acid.
  • the medium can be acidified with, e.g., an inorganic or organic acid, such as formic acid, sulfuric acid, a salt thereof (e.g., that provides an electrolyte), or a combination thereof.
  • the acidified aqueous medium can be an electrolyte.
  • the medium can be contained in a reactor that includes an anode (e.g., the counter electrode), a cathode (e.g., the working electrode), and a reference electrode (e.g., an Ag/AgCl electrode or a reversible hydrogen electrode).
  • the reactor can be any suitable reactor having any suitable shape, such that the method can be carried out as described herein.
  • the reactor can be a batch reactor.
  • the reactor can be a continuous flow reactor.
  • the muconic acid can be produced in any suitable way. In some embodiments, the muconic acid is commercially obtained. In some of
  • the muconic acid is produced from petroleum materials.
  • the muconic acid is produced from a microorganism or an enzyme, such as any suitable microorganism or enzyme.
  • the muconic acid can be produced by yeast or bacteria, such as any suitable yeast or bacteria.
  • the microorganism (e.g., yeast or bacteria) or enzyme can use any suitable organic material to generate the muconic acid, such as a carbohydrate (e.g., glucose), or such as an aromatic material (e.g., lignin).
  • the muconic acid is generated by yeast in a fermentation broth.
  • the fermentation broth can be any suitable fermentation broth.
  • the fermentation broth can include glucose and support the conversion of glucose into muconic acid by yeast, such as any suitable type of yeast that can perform the conversion.
  • the fermentation broth can include yeast nitrogen base.
  • the yeast nitrogen base can be substantially free of amino acids, ammonium sulfate, or a combination thereof.
  • the fermentation broth can include complete supplement mixture (CSM) uracil-dropout amino acid mix.
  • the method can include at least partially simultaneously fermenting the broth to form muconic acid from the yeast and hydrogenating muconic acid in the broth.
  • the cathode used in the reaction can utilize both high and low hydrogen overvoltage catalytic metals, e.g., lead or another metal such as platinum, vanadium, chromium, manganese, iron, cobalt, zinc, aluminum, titanium, zirconium, niobium, molybdenum, ruthenium, palladium, cadmium, indium, samarium, antimony, hafnium, tantalum, rhenium, iridium, gold, bismuth, tungsten, nickel, copper, silver, alloys thereof, or combinations thereof.
  • catalytic metals e.g., lead or another metal such as platinum, vanadium, chromium, manganese, iron, cobalt, zinc, aluminum, titanium, zirconium, niobium, molybdenum, ruthenium, palladium, cadmium, indium, samarium, antimony, hafnium, tantalum, rhenium,
  • the material used for the anode is not critical. Suitable anodes can include graphite, platinum, platinum-coated titanium, ruthenium oxide titanium oxide-coated titanium, or combinations thereof.
  • the anodic reaction can be the oxidation of water to produce oxygen gas.
  • the electric potential applied to the cathode with a respect to a reference electrode can be adjustable and can be maintained at about -0.1 to about -5 V, about -0.5 to about -3.0 V, about -0.5 to about -2.0 V, e.g., about -0.8 to -1.8 V, or about -0.1 or more, or less than, equal to, or greater than about -0.2,- 0.3, -0.4, -0.5, -0.6, -0.7, -0.8, -0.9, -1, -1.1 , -1.2, -1.3, -1.4, -1.5, -1.6, -1.7, -1.8, -1.9, -2, -2.1 , -2.2, -2.4, - 2.6, -2.8, -3, -3.2, -3.4, -3.6, -
  • the muconic acid starting material can be any suitable muconic acid.
  • the muconic acid can be ds,ds-muconic acid, trans, cis- uconic acid, trans, trans- uconic acid, or a combination thereof.
  • the muconic acid starting material is about 0 mol% to about 100 mol% cis,cis- muconic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the muconic acid starting material is about 0 mol% to about 100 mol% trans,cis- ucomc acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the muconic acid starting material is about 0 mol% to about 100 mol% trans,trans- muconic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can yield a product mixture that has any suitable composition.
  • the product can include 3- hexene-l,6-dioic acid (e.g., cis-3-hexene-l ,6-dioic acid, trans-3-hexene-l,6-dioic acid, or a combination thereof), 2-hexene-l,6-dioic acid (e.g. cis-3-hexene-l,6- dioic acid, trans-3-hexene-l ,6-dioic acid, or a combination thereof), adipic acid, or a combination thereof.
  • 3- hexene-l,6-dioic acid e.g., cis-3-hexene-l ,6-dioic acid, trans-3-hexene-l,6-dioic acid, or a combination thereof
  • the product of the electrocatalytic hydrogenation of the muconic acid can include 3-hexene-l ,6-dioic acid (e.g., cis, trans, or a combination thereof) in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% 3-hexene-l,6-dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% 3-hexene-l,6-dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1 , 1 , 2, 3,
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for 3-hexene-l,6-dioic acid, such as about 0% to about 100% (e.g., 0 mol% to about 100 mol% of the muconic acid hydrogenated can be 3-hexene-l,6-dioic acid), or about 0%, or about 0.001% or less, or less than, equal to, or greater than about 0.01 %, 0.1, 1, 2, 3, 4,
  • the product of the electrocatalytic hydrogenation of the muconic acid can include ds-3-hexene-l,6-dioic acid in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% ds-3-hexene-l,6- dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% ds-3-hexene-l ,6- dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for ds-3-hexene-l,6-dioic acid, such as about 0% to about 100%, or about 0%, or about 0.001 % or less, or less than, equal to, or greater than about 0.01 %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the product of the electrocatalytic hydrogenation of the muconic acid can include fraws-3-hexene- 1,6-dioic acid in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% fraws-3-hexene- 1,6-dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% trans-3- hexene- 1,6-dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1 , 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for trans-3 -hexene- 1 ,6-dioic acid, such as about 0% to about 100%, or about 0%, or about 0.001 % or less, or less than, equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the product of the electrocatalytic hydrogenation of the muconic acid can include 2-hexene- 1 ,6-dioic acid (e.g., cis, trans, or a combination thereof) in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% 2-hexene- 1,6-dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% 2-hexene- 1 ,6-dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1 , 1 , 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for 2-hexene- 1,6-dioic acid, such as about 0% to about 100%, or about 0%, or about 0.001% or less, or less than, equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the product of the electrocatalytic hydrogenation of the muconic acid can include ds-2-hexene- 1 ,6-dioic acid in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% ds-2-hexene- 1,6- dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% ds-2-hexene- 1 ,6- dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for ds-2-hexene- 1,6-dioic acid, such as about 0% to about 100%, or about 0%, or about 0.001 % or less, or less than, equal to, or greater than about 0.01 %, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the product of the electrocatalytic hydrogenation of the muconic acid can include fraws-2-hexene- 1,6-dioic acid in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% fraws-2-hexene- 1,6-dioic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% trans-2- hexene- 1,6-dioic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for fraws-2-hexene- 1 ,6-dioic acid, such as about 0% to about 100%, or about 0%, or about 0.001% or less, or less than, equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the product of the electrocatalytic hydrogenation of the muconic acid can include adipic acid in any suitable wt% or mol%.
  • the product can be about 0 wt% to about 100 wt% adipic acid, or about 0 wt%, or about 0.001 wt% or less, or less than, equal to, or more than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more, or about 100 wt%.
  • the product can be about 0 mol% to about 100 mol% adipic acid, or about 0 mol%, or about 0.001 mol% or less, or less than, equal to, or more than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more, or about 100 mol%.
  • the electrocatalytic hydrogenation of the muconic acid can have any suitable selectivity for adipic acid, such as about 0% to about 100%, or about 0%, or about 0.001% or less, or less than, equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the electrocatalytic hydrogenation of the muconic acid can be performed with any suitable percent conversion of the muconic acid.
  • the conversion of the muconic acid can be about 0.001% to about 100%, or about 0.001% or less, or less than, equal to, or greater than, about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the cathode can include any suitable material, such that the method can be carried out as described herein.
  • the cathode can include, or can be, one or more transition metals.
  • the cathode can include, or can be, at least one of Cu, Fe, Ni, Pd, Pt, Pd/C, Pb, Sn, Ti, Zn, or a combination thereof.
  • the cathode can include, or can be, one or more platinum group metals.
  • the cathode can include, or can be, lead.
  • the cathode can include, or can be, platinum.
  • the cathode can include, or can be, Ni,
  • the electrocatalytic hydrogenation can yield a product that includes adipic acid.
  • the adipic acid can be formed with any suitable selectivity, such as about 80% to about 100%, or about 90% to about 100%, or about 95% to about 100%, or about 80% or less, or less than, equal to, or greater than about 81%, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the cathode can include Cu, Fe, Pb, Sn,
  • the cathode can include or can be Pb.
  • the electrocatalytic hydrogenation can yield a product that includes trans-3 -hexene- 1,6-dioic acid.
  • the £raws-3-hexene-l,6-dioic acid can be formed with any suitable selectivity, such as about 40% to about 100%, about 80% to about 100%, or about 90% to about 100%, or about 95% to about 100%, or about 40% or less, or less than, equal to, or greater than about 45, 50, 55, 60, 65, 70, 75, 80, 81%, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • the muconic acid can be converted with any suitable percent conversion, such as about 40% to about 100%, about 80% to about 100%, or about 90% to about 100%, or about 95% to about 100%, or about 40% or less, or less than, equal to, or greater than about 45, 50, 55, 60, 65, 70, 75, 80, 81%, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • any suitable percent conversion such as about 40% to about 100%, about 80% to about 100%, or about 90% to about 100%, or about 95% to about 100%, or about 40% or less, or less than, equal to, or greater than about 45, 50, 55, 60, 65, 70, 75, 80, 81%, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93
  • the electrocatalytic hydrogenation of the muconic acid can occur with any suitable faradaic efficiency, such as about 2% to about 100%, or about 30% to about 100%, or about 2% or less, or less than, equal to, or greater than about 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% or more, or about 100%.
  • any suitable faradaic efficiency such as about 2% to about 100%, or about 30% to about 100%, or about 2% or less, or less than, equal to, or greater than about 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5,
  • the cathode can have any suitable catalytic turnover frequency, such as about 0.01 s "1 to about 120 s “1 , about 0.01 s “1 to about 60 s “1 , about 0.10 s “1 to about 35 s “1 , or about 0.01 s “1 or less, or less than, equal to, or more than about 0.1 s "1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1 , 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 s
  • the present invention provides a method of making a polymer.
  • the method can include performing an embodiment of the method of electrocatalytically hydro genating muconic acid described herein, and polymerizing one or more products thereof along with one or more other compounds to form a polymer.
  • the polymer can have any suitable structure.
  • the method includes polymerizing 2- hexene-l,6-dioic acid, the 3-hexene-l ,6-dioic acid, or a combination thereof, with another compound, to form a polymer, wherein the 2-hexene-l ,6-dioic acid and the 3-hexene-l,6-dioic acid are made by any suitable method and not necessarily by an embodiment of the method of electrocatalytically
  • the method of making a polymer can include performing an embodiment of the method of electrocatalytically hydrogenating muconic acid described herein to form 2-hexene- 1 ,6-dioic acid, the 3-hexene-l,6-dioic acid, the adipic acid, or a combination thereof.
  • the method can include polymerizing the 2-hexene- 1,6-dioic acid, the 3-hexene-l ,6-dioic acid, the adipic acid, or a combination thereof, with another compound, to form a polymer.
  • the method of making a polymer can include performing an embodiment of the method of electrocatalytically hydrogenating muconic acid described herein to form 2-hexene- 1 ,6-dioic acid, the 3-hexene- 1,6-dioic acid, adipic acid, or a combination thereof.
  • the method can include polymerizing the 2-hexene- 1 ,6-dioic acid, the 3-hexene- 1,6-dioic acid, the adipic acid, or a combination thereof, with a compound having the structure H 2 N-(Ci- C 2 o)alkylene-NH 2 , HO-(Ci-C 20 )alkylene-NH 2 , HO-(Ci-C 20 )alkylene-OH, a salt thereof, or a combination thereof, wherein the (Ci-C 2 o)alkylene group is substituted or unsubstituted, to form a polymer.
  • the polymerizing can form a polymer including a repeating group having the structure:
  • -A- is independently chosen from -NH- and -0-.
  • the polymerizing can form a polymer including a repeating group having the structure:
  • -A- is independently chosen from -NH- and -0-.
  • (Ci-C 2 o)alkylene-NH 2 is hexamethylenediamine, and the polymerizing forms a polymer including a repeating group having the structure:
  • the method can include forming adipic acid via an embodiment of the electrocatalytic hydrogenation of muconic acid.
  • the method can include polymerizing the adipic acid with another compound, to form a polymer.
  • the method can include polymerizing the adipic acid with a compound having the structure H2N-(Ci-C2o)alkylene-NH2 or a salt thereof, wherein the (Ci-C2o)alkyl group is substituted or unsubstituted, to form a polymer.
  • the compound having the structure H2N-(Ci-C2o)alkylene-NH2 can be hexamethylenediamine, wherein the polymer is nylon 6,6.
  • the polymerizing can form a polymer including a repe
  • the present invention provides a method of forming a polymer including polymerizing 2-hexene-l,6-dioic acid, the 3- hexene-l,6-dioic acid, or a combination thereof, with another compound, to form a polymer, wherein the 2-hexene-l,6-dioic acid and the 3-hexene-l ,6-dioic acid are not necessarily formed via an embodiment of the method of
  • the present invention provides a method of forming a polymer including polymerizing the 2-hexene- 1,6-dioic acid, the 3- hexene- 1,6-dioic acid, or a combination thereof, with a compound having the structure H2N-(Ci-C2o)alkylene-NH2 or a salt thereof, wherein the (Ci-C2o)alkyl group is substituted or unsubstituted, to form a polymer, wherein the 2-hexene- 1,6-dioic acid and the 3-hexene- 1,6-dioic acid are not necessarily formed via an embodiment of the method of electrocatalytically hydrogenating muconic acid.
  • the present invention provides a polymer.
  • the polymer need not be formed from the hydrogenation products of muconic acid.
  • the polymer can be any suitable polymer that has a structure that can be formed by polymerizing the products of an embodiment of the electrocatalytic hydrogenation of muconic acid described herein, wherein the polymer can be formed in any suitable way.
  • the polymer can include a repeating group having the structure:
  • -NH-(CH2)i-2o-NH- group can be substituted or unsubstituted.
  • -A- is independently chosen from -NH- and -0-.
  • the repeating group of the polymer can have the structure:
  • -NH-(CH2)i-2o-NH- group can be substituted or unsubstituted.
  • -A- is independently chosen from -NH- and - 0-.
  • the repeating group of the polymer can have the structure:
  • -A- is independently chosen from -NH- and -0-.
  • the repeating group of the polymer can have the structure:
  • Example 1-1 Electrocatalytic hydrogenation of muconic acid in 1% formic acid.
  • a 3/8" diameter lead wire was purchased from Rotometals
  • Electrocatalytic hydrogenation studies of muconic acid (MA) were carried out in a three-electrode electrochemical cell (1) depicted in FIG. 1.
  • the container (2) was about 2.54 cm in diameter and about 3.8 cm high.
  • the electrolyte level (3) shown is approximate.
  • Current was passed through an aqueous reaction medium (3) including 1 % formic acid in water (electrolyte) and varying concentrations of muconic acid.
  • the electrolyte was agitated via magnetic stirring using stir bar (4).
  • Scheme 3 provides the conversion, selectivity, and faradaic efficiency (e.g., electron efficiency) calculations where n are the number of electrons transferred, F is Faraday's constant, I is the current passed during the electrocatalytic hydrogenation at duration t.
  • HDA 3-hexene-l,6-dioic acid
  • a 3/8" diameter lead wire was purchased from Rotometals
  • Formic acid was purchased from Sigma (99%), trans,trans- muconic acid (98%) and cis,cis-muconic acid (>97%) were purchased from Aldrich.
  • D-Glucose was purchased from Fisher Scientific (BP350-1), yeast nitrogen base without amino acids and ammonium sulfate were purchased from BD Diagnostic Systems (DF0335-15-9), ammonium sulfate was purchased from Fisher Scientific (BP212R-1), and complete supplement mixture (CSM) of amino acids was purchased from MP Biomedicals (MP11451031).
  • Cis,trans- muconic acid was synthesized by allowing cis,cis-muconic acid to isomerize at room temperature in water for five days. All solutions were synthesized in Millipore water (18.0 ⁇ ). (1-2)(B). Fermentation.
  • the fermentation broth used was yeast synthetic complete (YSC) medium composed of 1.7-g/L yeast nitrogen base without amino acids and without ammonium sulfate; 5000 ppm ammonium sulfate; 20-g/L d-glucose; and the corresponding complete supplement mixture (CSM) uracil-dropout mix (e.g., a mixture including all standard amino acids except uracil).
  • YSC yeast synthetic complete
  • CSM complete supplement mixture
  • the fermentations were carried out for 5 days in baffled flasks at 30 °C and 250 rpm to convert glucose to muconic acid.
  • Kimwipe and the coiled platinum wire was sonicated in water.
  • the reference, counter, and working electrode were subsequently inserted into the three- electrode electrochemical cell containing the 11 mL of the aqueous reaction medium.
  • a constant voltage of -1.5 V vs. Ag/AgCl in 3M NaCl was applied to the cell for 50 min to 2.0 h.
  • the solution was left at ambient temperature and pressure through the reaction.
  • 0.5 mL of reaction medium was taken at varying intervals throughout the reaction to analyze product composition.
  • Bio-based unsaturated nylon 6,6 (unsaturated polyamide 6,6) was finally obtained by polymerization of 3- hexenedioic acid with hexamethylenediamine (HMD A), to yield the desired UPA 6,6, demonstrating the integrated design of bio-based polyamides from glucose.
  • FIG. 3 illustrates the integrated conversion of glucose to UPA 6,6.
  • the catalytic integration was enabled by the compatibility of the process parameters. Replacing conventional high-pressure hydrogenation by direct ECH promoted a seamless flow between the processes. This removed the need of intermediate separation and allowed the use of the broth water, salts, and impurities as an electrolyte and hydrogen source.
  • Example 2-1 Electrocatalytic hydrogenation.
  • Electrocatalytic hydrogenation experiments were performed in 11 mL of reacting medium with a stir bar at 700 rpm. During the chronoamperometry experiments, 0.5 mL samples of the reaction medium were taken at 5 min, 15 min, 30 min, and 60 min for analysis.
  • the method was as follows: 0.35 ml min "1 of 4% Solution A and 96% of Solution B for 4.5 min followed by ramping A to 50% (50% B) and maintained until min 6. The composition of the mobile phase was reverted to 4% Solution A and 96% Solution B and maintained for 8 additional min. The column was maintained at 45 °C and the sample reservoir at 15 °C.
  • ACS grade cis,cis-MA was used to synthesize cis,trans-MA by heating in water at 75 °C for 25 min.
  • trans-HOA Sigma, St Louis, MO
  • cis,trans-MA were used for UPLC calibration and as references. Retention times of cis, trans-MA and trans- HDA are 6.4 min and 4.0 min and were analyzed at 295 nm and 231 nm respectively. Conversions and selectivities, were calculated with the following equations:
  • ECH of the fermentation medium was performed as follows.
  • a fermentation broth containing MA was produced from a genetically engineered strain of diploid yeast, yielding 14 mgMA per g g i U cose, the highest yield among the aromatic amino acid-based metabolites that have been produced in yeast in batch fermentation.
  • the fermentation broth was subsequently hydrogenated in a three-electrode electrochemical cell, as illustrated in FIG. 1. Electrocatalysis was preferred over conventional high- pressure hydrogenation as hydrogen is produced in situ by water splitting, the reaction occurs under ambient temperature and pressure, and the charge on the electrode surface can mitigate poisoning. In this configuration, hydrogen production and MA hydrogenation take place simultaneously at the cathode (Scheme 4), allowing a seamless ECH.
  • FIGS. 4A-B illustrate conversion of MA to HDA in the fermentation broth using electrocatalytic hydrogenation.
  • the hydrogen necessary for the reaction is generated in situ (Had) at the surface of the Pb electrode.
  • FIG. 4A conversion of MA and average selectivity to the desired product showed no signs of catalyst deactivation when repeating the reaction five successive times (runs 1-5).
  • FIG. 4B illustrates MA and HDA conversion and selectivity for the ECH of the doped (pH 2.0, -1.5 V) fermentation broth.
  • Lead (Pb) was chosen as a catalyst based on its Earth abundance, low cost, and potential stability in the presence of sulfur.
  • the resistance to impurities allowed the significant simplification of the hydrogenation reaction by placing the fermentation broth directly in the electrochemical reactor.
  • the broth contained whole yeast cells, unspent salts, and biogenic impurities coming from cellular metabolism and lysis.
  • the ECH was then allowed to proceed at room temperature and atmospheric pressure for 1 hour by applying a potential of -1.5 V vs. Ag/AgCl on a 10 cm 2 lead rod, resulting in 95% MA conversion with 81% selectivity to HDA.
  • FIGS. 5A-B illustrate MA conversion and HDA selectivity versus reaction time of ECH of model solutions of MA with varying pH
  • the pH in the solution was changed by adding various ratios of K2SO4 and H2SO4 to maintain the ionic conductivity.
  • An ECH of the solution was run at -1.5 V for 1 h with the Pb catalyst.
  • FIG. 6 illustrates l U NMR spectra, 600 MHz, in D 2 0, of HDA subjected to -1.5 V for 2 h before (A) and after (B) reaction. Decomposition products are shown to form after the reaction.
  • the l H nuclear magnetic resonance (NMR) analysis of the HDA model solution after ECH revealed that the observed decrease in selectivity as the reaction proceeded was due to the formation of decomposition products through secondary reactions.
  • FIGS. 7A-B illustrate MA conversion and HDA selectivity versus reaction time during ECH of model solutions of MA at varying potentials.
  • the pH was fixed at 2.0 by adding 0.5 M H2SO4 to a solution of water and MA.
  • An ECH of the solution was run for 1 h with the applied potentials.
  • a potential of -1.5 V and a pH of 2.0 offered a compromise between conversion and selectivity.
  • FIG. 8 illustrates a l U NMR of irarcs-3-hexenedioic acid (?3HDA) extracted from the fermentation broth (1) before crystallization and (2) after crystallization
  • Example 2-2 Polymer synthesis and characterization. (2-2)(A). Materials and methods.
  • HDA and hexamethylenediamine (HMDA) was adapted from the synthesis of nylon 6,6.
  • traws-HDA TCI America
  • HMDA hexamethylenediamine
  • TCI America traws-HDA
  • the resulting solution was heated in a round bottom flask at 60 °C.
  • the liquid was decanted from the precipitated salt.
  • the precipitated salt was subsequently washed with methanol, decanted, and left to dry in a fume hood.
  • the solid was then mixed at a 0.86 mass ratio with deionized water.
  • the resulting solution was put in an aluminum weigh pan and heated at 7.5 °C min "1 to 250 °C in a tube furnace under flowing ultra-high purity nitrogen. The sample dwelled at the temperature for 30 min before cooling. It was not uncommon during the synthesis of UPA 6,6 to produce a slightly yellow colored polymer. The same synthesis procedure was applied to adipic acid and HMD A to form nylon 6,6.
  • Triple detection analysis consisted of a refractive index, right angle and low angle light scattering, and a four-capillary differential viscometer in series (Table 5 , FIG. 10).
  • the absolute molecular weight of nylon 6,6 and UPA 6,6 was calculated using a dn/dc value of 0.235 mL g "1 .
  • TGA Thermal Gravimetric Analysis
  • DSC Differential Scanning Calorimetry
  • X-ray powder diffraction X-ray powder diffraction
  • a SCINTAG XDS2000 powder diffractometer equipped with a Cu source ( ⁇ 1.54 A) and a Kevex Peltier cooled silicon detector was used to test the nylon 6,6 and the UPA 6,6.
  • HDA has been used as a precursor to generate dodecanedioic acid, a monomer of nylon 6,12, and to produce polyester ethers with biomedical applications.
  • This polyamide has the advantage of having an extra double bond in its backbone that can be used to incorporate additional functionality.
  • the corresponding saturated nylon 6,6 was synthesized using adipic acid and HMDA through the same procedure in an attempt to compare the conventional petrochemical-based nylon 6,6 and the bio-based UPA 6,6 polymers.
  • FIG. 9A illustrates 1) nylon 6,6 and 2) UPA 6,6, for which petroleum-based adipic acid was substituted with HDA.
  • FIG. 9B polymers based on blends of HDA and adipic acid were also achieved (FIG. 9B) to potentially enable different levels of crosslink and functionality e.g. for tuned hydrophobicity and hydrophilicity.
  • FIG. 9B illustrates polymer blends of adipic acid and HDA, with percentages based on molar ratios of adipic acid and HDA reacted with a 1 :1 mol ratio of HMDA.
  • FIG. 10 illustrates an overlay from GPC elution traces obtained from RI detector and Log MW (diagonal lines) versus retention volume for nylon 6,6 and UPA 6,6.
  • FIG. 11 illustrates thermal gravimetric analysis of nylon 6,6 and UPA 6,6. Nylon 6,6 showed 50% mass loss at 456 °C and UPA 6,6 showed a 50% mass loss at 463 °C.
  • FIG. 10 illustrates an overlay from GPC elution traces obtained from RI detector and Log MW (diagonal lines) versus retention volume for nylon 6,6 and UPA 6,6.
  • FIG. 11 illustrates thermal gravimetric analysis of nylon 6,6 and UPA 6,6. Nylon 6,6 showed 50% mass loss at 456 °C and UPA 6,6 showed a 50% mass loss at 463
  • FIG. 12 illustrates differential scanning calorimetry results for nylon 6,6 and UPA 6,6 (exothermic up), which displayed melting temperature of 255 °C for nylon 6,6 and 60 °C for UPA 6,6.
  • the material shows classical Rouse-like behavior, common in linear low molecular weight polymer melts.
  • the material shows classical Rouse-like behavior, common in linear low molecular weight poly
  • Electrocatalytic hydrogenation is used to hydrogenate cis, trans-
  • MA ciMA to two monomers, adipic acid, and fraws-3-hexenedioic acid, used for the production of nylon, nylon derivatives, and poly(ester ethers).
  • the electrocatalytic hydrogenation considers a wide range of early, late, and post transition metals (Cu, Fe, Ni, Pb, Pd/C, Sn, Ti, and Zn) with low and high hydrogen overpotentials; this selection possesses varying degrees of metal hydrogen binding strengths.
  • the binding strength was determined to be an important factor for the conversion rate, faradaic efficiency, and selectivity of the hydrogenation. Selectivities are also discussed in relation to thermodynamic data, which suggests the possibility to tune the kinetics of the reaction to allow for the variable production of multiple monomers.
  • Pb and Pd/C were identified as potential catalysts for the production of fraws-3-hexenedioic acid and adipic acid, respectively.
  • fraws-3-Hexenedioic acid (?3HDA) is a bio-based chemical that has been rarely observed and only in low yields during the semi- hydrogenation of MA under pressurized H 2 .
  • Further analysis of Pb and Pd/C revealed turnover frequencies of 5.6 s "1 and 0.1 s "1 , respectively.
  • Electrocatalysis The electrochemical studies were conducted in a conventional single compartment three-electrode glass cell using a BioLogic potentiostat (VSP-300). All potentials in this part are in reference to the reversible hydrogen electrode (RHE).
  • Initial experiments to determine reaction schemes and product decomposition were performed with 11 ml solution of muconic acid dissolved in 0.01 M sulfuric acid electrolyte (H2SO4).
  • the cell was equipped with a Pt counter electrode (Biologic), an Ag/AgCl in NaCl reference electrode (Biologic), and a 10 cm 2 Pb rod (Rotometals, 99.9% purity) working electrode.
  • the solutions were magnetically stirred at 700 rpm with a PTFE flea stir bar.
  • a PTFE flea stir bar During chronoamperometry experiments, 0.5 ml aliquots of the reaction medium were withdrawn periodically.
  • ciMA 3.52 mM ciMA and 0.26 M formic acid (electrolyte).
  • ciMA was prepared by heating ccMA at 75 °C for 25 min. The cell was equipped with an Ag/AgCl in sat. KC1 reference electrode (Pine) and Pt counter electrode (Pine Research Instruments). The working electrodes were purchased as follows: Sigma (5wt% Pd/C), Flinn scientific (Cu, Fe, Pb, Zn), Science Company (Ni), and
  • the solvation component for the acidity calculations were done as follows.
  • the solvation free energies in water at 298 K were calculated using the self-consistent reaction field approach with the COSMO parameters, as implemented in the Gaussian 03 using the B3LYP/DZVP2 gas phase geometries.
  • the COSMO (B 3 LYP/DZ VP2) calculations in Gaussian 03 the radii developed by Klamt and co-workers were used to define the cavity.
  • a dielectric constant of 78.39 corresponding to that of bulk water was used in the COSMO calculations.
  • the solvation energy is reported as the electrostatic energy (polarized solute - solvent).
  • the error in the absolute calculated pK a of CH3COOH is 3.0 pK a units using a value for the free energy of solvation of the proton of -264.3 kcal/mol.
  • FIG. 15 illustrates concentrations of MA isomers over time at low pH. Periodic analysis by l H NMR revealed that ccMA fully isomerizes into ctMA within 3 days. The composition of the solution
  • ECH and the hydrogen evolution reaction share the first elemental step (Volmer step), where protons from the solution are reduced to form adsorbed hydrogen atoms
  • thermodynamic data is widely available for HER.
  • muconic acid is not a common reactant and, like many biorenewable molecules, thermodynamic data is not available in the open literature. Therefore, the thermodynamic properties of all the molecules susceptible to form were calculated as well as the heats of formation and the free energies associated with all the hydrogenation reactions that may take place during ECH (Tables 7-8). In all cases, a two-step reaction was considered where MA is first hydrogenated to the corresponding mono-unsaturated di-acid (cis and trans isomers of 2- and 3-HDA) before further hydrogenation to AA (Table 8).
  • FIG. 16 illustrates theoretical potentials for the formation of hydrogen (HER), c3HDA, ?3HDA, c2HDA, ?2HDA, and AA from ciMA as a function of pH.
  • HER hydrogen
  • c3HDA ?3HDA
  • c2HDA ?2HDA
  • AA AA from ciMA as a function of pH.
  • the potentials for ECH are higher than for HER over the pH range 0-14.
  • FIG. 16 implies that ECH reactions are thermodynamically favored over HER, regardless of pH.
  • the plot also reveals little difference between f2HDA, ?3HDA, and AA, meaning that selective synthesis of any of these 3 chemicals by fine tuning the reaction kinetics may be possible.
  • the compounds 2HDA and 3HDA could be useful monomers for polyester and polyamide synthesis based on their structural resemblance to adipic and fumaric acids.
  • Table 7 Heats of formation (gas and liquid), boiling point, and gas phase acidities (AG gas ) at G3MP2 level in kcal mol "1 and pK a (relative to acetic acid).
  • ccMA, ctMA, and ??MA correspond to cis,cis-, cis rans-, and trans rans- uconic acid
  • c2HDA, ?2HDA, c3HDA, and ?3HDA designate the cis (c) and trans (t) isomers of 2-hexenedioic acid (2HDA) and 3-hexenedioic acid (3HDA);
  • AA corresponds to adipic acid.
  • ccMA, ctMA, and ffMA correspond to cis,cis-, cis rans-, and trans rans- uconic acid
  • c2HDA, ?2HDA, c3HDA, and ?3HDA designate the cis (c) and trans (t) isomers of 2-hexenedioic acid (2HDA) and 3-hexenedioic acid (3HDA)
  • AA corresponds to adipic acid.
  • FIG. 17 illustrates a volcano plot showing the current exchange densities (HER activities) achieved as a function of the free energy of hydrogen adsorption AGH of the metals.
  • HER activities current exchange densities
  • Optimal HER activity is achieved for metals with AGH ⁇ 0.
  • the colors indicate the main product formed during ECH.
  • the highest exchange current densities (high HER activity) were observed for metals with a free energy for hydrogen binding AGH ⁇ 0.
  • Metals that bind hydrogen more strongly (AGH ⁇ 0) or more weakly (AGH > 0) are significantly less active and adsorbed hydrogen atoms are therefore more likely to be involved in
  • FIGS. 18A-0 illustrate conversion and selectivity during ECH of ctMA in 1 % formic acid solution with low hydrogen
  • FIGS. 18A, B, and C used Cu, FIGS. 18D, E, and F used Fe, FIGS. 18G, H, and I used Ni, FIGS. 18 J, K and L used Pd foil, and FIGS. 18M, N, and O used Pd/C (5 wt% Pd on C).
  • Platinum group metals specifically Ni and Pd/C, were the only catalysts that produced AA. ECH with Pt was not attempted as platinum is a very active HER catalyst. Pd/C (5 wt% Pd on C) was the best ECH catalyst of this group as it produced AA with 92% selectivity. The fraction of unknown or undetected products calculated based on the carbon balance decreased over time and when increasing the potential from -1.12 V to -1.72 V, thus indicating that ctMA decomposition was minimal and probably only occurred in the early stages of the electrocatalytic reaction. For low overpotential metals with AGH ⁇ 0, the ECH rate was low compared to HER and the ctMA conversion after 1 h reached 7% at best.
  • FIGS. 19A-L illustrate conversion and selectivity of ECH of ctMA in 1 % formic acid solution with high hydrogen overpotential metals at -1.12 V (A, D, G, J), - 1.72 V (B, E, H, K), and corresponding faradaic efficiencies (C, F, I, L).
  • FIGS. 19A, B, and C used Pb
  • FIGS. 19D, E, and F used Sn
  • FIGS. 19G, H, I used Ti and FIGS. 19J, K, and L used Zn.
  • Metals that deviate further from ideal HER catalysts and present large IAGHI were more selective towards ?3HDA and showed faster ECH rates than low hydrogen overpotential metals.
  • ??MA concentration decreased as ctMA conversion reached 80%, thus confirming that ??MA is an intermediate in the hydrogenation of ctMA to ?3HDA. This intermediate was not observed at higher potential (-1.12 and -1.72 V) likely due to faster kinetics or a shift in the rate determining step (FIGS. 19A-L).
  • the faradaic efficiency of a reaction is an important measure of hydrogen utilization and a common way to assess the performance of electrocatalysts. While this figure is an important metric, it is highly dependent on reactant concentration, applied potential, and pH of the reacting medium.
  • Another important figure of merit of a catalyst is the turnover frequency (TOF). Despite being a fair value to compare catalysts, TOFs are unusual in
  • FIGS. 20A-C illustrate light microscope images of the Pb electrode strip (a) after cleaning with a kimwipe, (b) after
  • FIGS. 21A-C illustrate conversion (A), selectivity (B), and faradaic efficiency (C) of ECH of ctMA with electro-polished Pb at -1.17 V in a 1 % formic acid solution.
  • the TOF was of about 6 s "1 (rounded from 5.6 s "1 ) in the early stages of the catalytic tests (FIG. 21C). This value seems reasonable considering that it is not based on the ECSA but on the geometric surface area of the electrode.
  • FIGS. 22A-D illustrate (A) Cyclic voltammetry of 5wt% Pd/C catalyst in 0.5 M NaOH (the peak below the horizontal line is integrated to determine the ECSA); (B) conversion and selectivity of ECH of ctMA in 1% formic acid solution at -1.17 V; (C) the corresponding Faradaic efficiency; and (D) turn over frequency of Pd/C catalyst.
  • the electrochemically active surface area of Pd/C was calculated through the electrochemical oxidation and reduction of Pd in a 0.5 M NaOH solution. In this technique, a monolayer of Pd is oxidized and subsequently reduced. The reduction peak at ca. -1.0 V is then integrated, the electrochemical double layer is subtracted, and the
  • electrochemically active surface area is calculated using a reference value for Pd of 405 cm “2 , and 1.27xl0 15 atoms cm “2 (FIG. 22A).
  • the value obtained for the Pd/C electrocatalyst was 1.04xl0 "7 molpd mgcat "1 , which corresponds to a dispersion of 22+2%.
  • Pd/C exhibited a TOF of 0.15 s "1 during the ECH of ciMA (FIG. 22D).
  • a TOF of 30 s "1 was calculated for Pd/C used for the high pressure hydrogenation of MA to AA. The difference is likely due to the high HER activity of Pd and active site blocking by adsorbed hydrogen.
  • FIGS. 23A-F illustrate ctMA and ?3HDA concentration profiles during simultaneous fermentation and ECH.
  • ECH was performed in the fermentation broth between 72-74 h.
  • a potential of -1.5 V vs. Ag/AgCl was applied to the working electrode during the reaction duration.
  • the working electrodes used in this study corresponds to (A) Fe, (B) Ni, (C) Pb, (D) Sn, and (E) Zn.
  • (F) corresponds to fermentation in absence of ECH.
  • Embodiment 1 provides an electrocatalytic method to prepare 3- hexene-l,6-dioic acid, 2-hexene-l,6-dioic acid, adipic acid, or a combination thereof, from muconic acid, the method comprising:
  • a catalytic cathode in a reactor comprising an aqueous acidic solution comprising muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydro genate the muconic acid to yield a product comprising 3- hexene-l,6-dioic acid, 2-hexene-l,6-dioic acid, adipic acid, or a mixture thereof.
  • Embodiment 2 provides the method of Embodiment 1, wherein passing the current through the cathode yields 3-hexene-l ,6-dioic acid.
  • Embodiment 3 provides the method of any one of Embodiments
  • Embodiment 4 provides the method of any one of Embodiments
  • muconic acid is ds,ds-muconic acid, trans, cis-muconic acid, trans, trans-muconic acid, or a combination thereof.
  • Embodiment 5 provides the method of any one of Embodiments
  • Embodiment 6 provides the method of any one of Embodiments
  • 2-hexene-l,6-dioic acid is ds-2-hexene- 1 ,6-dioic acid, trans-2- hexene-l,6-dioic acid, or a combination thereof.
  • Embodiment 7 provides the method of any one of Embodiments
  • 3-hexene-l,6-dioic acid is ds-3-hexene-l,6-dioic acid, trans-3- hexene-l,6-dioic acid, or a combination thereof.
  • Embodiment 8 provides the method of any one of Embodiments
  • Embodiment 9 provides the method of any one of Embodiments
  • the cathode comprises at least one of Cu, Fe, Ni, Pd, Pt, Pd/C, Pb, Sn, Ti, Zn, or a combination thereof.
  • Embodiment 10 provides the method of any one of Embodiments 1-9, wherein the cathode comprises one or more platinum group metals.
  • Embodiment 11 provides the method of any one of Embodiments
  • the cathode consists of one or more platinum group metals.
  • Embodiment 12 provides the method of any one of Embodiments
  • the cathode comprises Ni, Pd, Pt, or a combination thereof.
  • Embodiment 13 provides the method of Embodiment 12, wherein the hydrogenation yields adipic acid.
  • Embodiment 14 provides the method of any one of Embodiments
  • Embodiment 15 provides the method of any one of Embodiments
  • the cathode comprises Pd/C, wherein the hydrogenation yields adipic acid with a selectivity of about 80% to about 100%.
  • Embodiment 16 provides the method of any one of Embodiments
  • the cathode comprises Cu, Fe, Pb, Sn, Ti, Zn, or a combination thereof.
  • Embodiment 17 provides the method of Embodiment 16, wherein the method yields fraws-3-hexene-l,6-dioic acid.
  • Embodiment 18 provides the method of any one of Embodiments
  • Embodiment 19 provides the method of any one of Embodiments
  • the cathode comprises Pb
  • the method yields trans-3- hexene-l,6-dioic acid with a selectivity of about 80% to about 100% and with a conversion of about 80% to about 100%.
  • Embodiment 20 provides the method of any one of Embodiments
  • Embodiment 21 provides the method of any one of Embodiments
  • Embodiment 22 provides the method of any one of Embodiments
  • Embodiment 23 provides the method of any one of Embodiments
  • the cathode comprises one or more transition metals.
  • Embodiment 24 provides the method of any one of Embodiments
  • cathode consists of one or more transition metals.
  • Embodiment 25 provides the method of any one of Embodiments
  • aqueous acidic solution comprises an organic acid, a mineral acid, a salt thereof, or a combination thereof.
  • Embodiment 26 provides the method of any one of Embodiments
  • aqueous acidic solution comprises formic acid, sulfuric acid, a salt thereof, or a combination thereof.
  • Embodiment 27 provides the method of any one of Embodiments
  • the current is generated by applying a voltage of about -0.5 to about -3.0 volts with respect to an Ag/AgCl reference electrode or with respect to a reversible hydrogen electrode.
  • Embodiment 28 provides the method of any one of Embodiments
  • Embodiment 29 provides the method of any one of Embodiments 1-28, wherein the method converts the muconic acid to the £raws-3-hexene-l,6- dioic acid at a selectivity of about 80% to about 100%.
  • Embodiment 30 provides the method of any one of Embodiments
  • Embodiment 31 provides the method of any one of Embodiments
  • Embodiment 32 provides the method of any one of Embodiments
  • Embodiment 33 provides the method of any one of Embodiments
  • Embodiment 34 provides the method of any one of Embodiments
  • Embodiment 35 provides the method of any one of Embodiments 1-34, wherein during the hydrogenation the cathode has a catalytic turnover frequency of about 0.01 s "1 to about 120 s "1 .
  • Embodiment 36 provides the method of any one of Embodiments
  • the cathode has a catalytic turnover frequency of about 0.10 s "1 to about 35 s "1 .
  • Embodiment 37 provides the method of any one of Embodiments
  • aqueous solution comprises an acidic fermentation broth comprising the muconic acid.
  • Embodiment 38 provides the method of any one of Embodiments
  • the fermentation broth comprises glucose and supports the conversion of glucose into muconic acid by yeast.
  • Embodiment 39 provides the method of any one of Embodiments
  • Embodiment 40 provides the method of Embodiment 39, wherein the yeast nitrogen base is substantially free of amino acids, ammonium sulfate, or a combination thereof.
  • Embodiment 41 provides the method of any one of Embodiments
  • the fermentation broth comprises ammonium sulfate.
  • Embodiment 42 provides the method of any one of Embodiments
  • the fermentation broth comprises complete supplement mixture (CSM) uracil-dropout amino acid mix.
  • CSM complete supplement mixture
  • Embodiment 43 provides the method of any one of Embodiments
  • the method comprises at least partially simultaneously fermenting the broth to form muconic acid and hydrogenating muconic acid in the broth.
  • Embodiment 44 provides the method of any one of Embodiments
  • Embodiment 45 provides the method of any one of Embodiments
  • C 2 o)alkylene group is substituted or unsubstituted, to form a polymer.
  • Embodiment 46 provides the method of any one of Embodiments 1-45, further comprising polymerizing the adipic acid with
  • hexamethylenediamine wherein the polymer is nylon 6,6.
  • Embodiment 47 provides the method of any one of Embodiments
  • Embodiment 48 provides the method of any one of Embodiments
  • Embodiment 49 provides the method of Embodiment 48, wherein the polymerizing forms a polymer comprising a repeating group having the structure:
  • Embodiment 50 provides the method of any one of Embodiments
  • Embodiment 51 provides the method of any one of Embodiments
  • Embodiment 52 provides the method of any one of Embodiments
  • polymerizing the adipic acid with hexamethylenediamine wherein the polymerizing forms a polymer comprising a repeating group having the structure:
  • Embodiment 53 provides an electrocatalytic method to prepare adipic acid from muconic acid, the method comprising:
  • a catalytic cathode comprising Pd on carbon
  • the catalytic cathode is in a reactor comprising an aqueous acidic solution comprising muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid so as to yield a product comprising adipic acid with a selectivity of about 40% to about 100%.
  • Embodiment 54 provides an electrocatalytic method to prepare iraw5-3-hexene-l ,6-dioic acid from muconic acid, the method comprising: passing current through a catalytic cathode comprising Cu, Fe, Pb, Sn, Ti, Zn, or a combination thereof, wherein the catalytic cathode is in a reactor comprising an aqueous acidic solution comprising muconic acid, a supporting electrolyte, and an anode, so as to generate atomic hydrogen on the cathode surface in an amount effective to hydrogenate the muconic acid so as to yield a product comprising ?raws-3-hexene-l,6-dioic acid with a selectivity of about 50% to about 100%.
  • Embodiment 55 provides a method of forming a polymer, comprising:
  • Embodiment 56 provides a method of forming a polymer, comprising:
  • Embodiment 57 provides a polymer comprising a repeating group having the structure:
  • Embodiment 58 provides the polymer of Embodiment 57, wherein the repeating group has the structure:
  • Embodiment 59 provides the polymer of any one of
  • -A- is independently chosen from -NH- and - 0-.
  • Embodiment 60 provides a polymer comprising a repeating group having the structure:
  • Embodiment 61 provides the method or polymer of any one any combination of Embodiments 1-60 optionally configured such that all elements or options recited are available to use or select from.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne divers modes de réalisation d'une hydrogénation électrocatalytique de l'acide muconique ainsi que des polymères formés à partir des produits de réaction ainsi obtenus. Plus précisément, l'invention concerne un procédé électrocatalytique pour la préparation de 3-hexène -1,6-acide dioïque, 2-hexène -1,6-acide dioïque, de l'acide adipique, ou une combinaison de ceux-ci, à partir d'acide muconique. Le procédé peut consister à faire passer un courant à travers une cathode catalytique dans un réacteur comprenant une solution aqueuse acide comprenant de l'acide muconique, un électrolyte de support, et une anode, de manière à générer de l'hydrogène atomique sur la surface de la cathode dans une quantité efficace pour hydrogéner l'acide muconique afin d'obtenir un produit comprenant de l'acide hexène-3-1,6-dioïque, de l'acide hexène-2 -1,6-dioïque, de l'acide adipique, ou un mélange de ceux-ci.
PCT/US2015/059974 2014-11-10 2015-11-10 Hydrogénation électrocatalytique de l'acide muconique Ceased WO2016077361A1 (fr)

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US10465043B2 (en) 2015-11-10 2019-11-05 Iowa State University Research Foundation Electrochemical isomerization of muconic acid
US10633750B2 (en) 2014-11-10 2020-04-28 Iowa States University Research Foundation, Inc. Electrocatalytic hydrogenation of muconic acid
US10793673B2 (en) 2015-11-10 2020-10-06 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11078139B1 (en) 2019-09-04 2021-08-03 The United States Of America, As Represented By The Secretary Of The Navy Cyclopentadiene fuels

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US20240254283A1 (en) * 2020-09-21 2024-08-01 Iowa State University Research Foundation, Inc. Base-catalyzed isomerization of muconic acid derivatives
CN116426968B (zh) * 2023-03-31 2025-08-01 北京化工大学 金属掺杂锡氧化物及其制备方法与应用

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US10633750B2 (en) 2014-11-10 2020-04-28 Iowa States University Research Foundation, Inc. Electrocatalytic hydrogenation of muconic acid
US10465043B2 (en) 2015-11-10 2019-11-05 Iowa State University Research Foundation Electrochemical isomerization of muconic acid
US10793673B2 (en) 2015-11-10 2020-10-06 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11401377B2 (en) 2015-11-10 2022-08-02 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11976169B2 (en) 2015-11-10 2024-05-07 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US12180338B2 (en) 2015-11-10 2024-12-31 Iowa State University Research Foundation, Inc. Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine
US11078139B1 (en) 2019-09-04 2021-08-03 The United States Of America, As Represented By The Secretary Of The Navy Cyclopentadiene fuels

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